Ozonization products of terpene alcohols and method of producing



Patented May Z S, 1935" a f a v 2,002,583' V I ozomz TroNrnoDUoTs or TERPENE I ALooHoL's AND .DUCINGW,

V METHOD; OF PRO- Lanning Parke Rankin, Norton, Kans., assignor a] p to Hercul'es Powder" Company, Wilmington,

Del., a corporation of Delaware v No Drawing; .Qriginalap'plication February 'z l,

, 1923, Serial N0; 256,-802.' Divided and this an pli'cation 'October'lii, 1933, Serial No. 694,114

12 Claims. (01. 260- 167) p My invention relates to ozonization products of terpene alcohols and method of producing the same; The compositionaccording to my inven-f tion is adaptable foruse, for example; as an oxidizing agent, a solvent or colloiding agent for nitrocellulose, thus making itavailable as an CwH-rzOI-I having, one double bond, asfor example, a terpineol, as alpha-terpineol, beta-terpineolanclthelike, terpinenol, or mixtures there- V of, whichhavebeen ozorlized or which have been ozonized and thenpartially decomposed by the application of heat after oz'onization.

; In the production offthe composition in ac cordance with, my invention, for example, com

mercial liquid technical terpineol" comprising a mixture of isomeric terpineols', pure crystalline alpha-terpineol, melting point33." C.,-35 0., and

which when melted will remain liquid throughout ozonization, or a pine-oil out, forexamplaa cut wboiling largely within about the. range 215 C.-220 C. and containing about 7 5% alpha= terpineol, may be ozonizedg'for example,.by pass: ing through it oxygen or air or other gas con-- tain'ingozonejor by} addingto it a liquid as, for example, carbon tetrachloride containing ,ozone.

The character. of the ozonized product will be alfected to some extent bythe methodof ozoniza tion and by'the temperature of ozonization which may beeffected by a temperature within "about j the range 0 C. CL, though the temperature" .is desirably maintained'within the more limitedrange 20"C.50 C. 7

.When the desired" ozonization is. effected, the ozonized product is heat-treated, by the'direct application: of heat or'by' steam' distillation. on

' heating the ozonized product to say, a tempera.-

aldehydes, acid and ketones; the presence-of the latter makes it an excellent solvent for nitrocellulose. In effecting heat treatment of the tilled.

As a'more specific example of the production of the composition inaccordance with my invention from, for example, alpha-terpineol, say

about two liters of crystalline alpha-terpineol}. suitably melted, are ozonized with oxygen con-x taining about 20 milligrams of ozone per liter zed product, it may be partially steam dis-.

fora period or twenty four hours at a temperature-of about 30? C. 1 The ozonized oxygen is perierably passed into the alpha-terpineolat the rateof about two'liters per minute. The ozonized' product obtained willnotgbe completely ozonized, but will be substantially more viscous than the originalalpha-terpineol and will have an-acid number of about It anda. saponification number of about 70 as compared with il for the corresponding values of the original alpha-terpineol." The ozonized product will have an iodin fiberating value, such that one gram or the ozonized product will liberate slowly morethan 0;.25 grams ofiodin from a solution of potassium iodide. If desired, the period of 'ozonization'may be'p'ro-f longed beyond twenty-four ;hourswith more complete ozonization and yield of a product having increased viscosity anda higher i'odin liberating value against potassiumiodide solutions On; ozonization of the terpineolg the molecule of ozone entersthe terpineolmolecule at the double bond in chains of three: oxygen atoms, and some oxidation and polymerization of the terpineol moleculeioccurs. Ozonization convertsthe: terpineol intoa. strong oxidizing agent, the acid number'varying from 1 to-40 andthesaponification number may .reach or higher.- The ozonized product in addition to its'power as an oxidizing agent, may be ofuse as a dryingoil and will have-acolloiding efiect on nitrocellulose. When the ozonization of they terpineol; as for example, technical terpineol, is effected, the ozonized-productisdesirablyheat-treated, as has been indicated by the direet-applieationof heat; or by distillation with steam. I-hef decomposi-- tion of the ozonizedterpineol results in the for mation ofa producteontainingaldehydes, acids and ketones; the presence of the latterincreases its, solvent. power on nitrocellulose. 'In. effecting heat treatment of the ozonizdi product, itfmaybe steam distilled and the decomposed product resultant from distillation or the application of heat may be given an alkali" wash for the separation of acidic compounds when suchiarerundesir able. L l H Aslan example oi the. production at the-composition-resulting from heattreatment of the ozonizedproduct in accordance with my invention, '100--g-.of" the liquid tepineol: of commerce. may b'e'o'zonized' ata temperature. of about 2570;. for: 8' hours with oz'onize'd oxygen containing about "20" "milligrams erdzoh" per litre. The

ozonized product is then subjected to steam distillation and about 20% distilled off as unaltered I I readily colloid nitrocellulose.

terpineol leaving a residual product which will Where it is desired to remove acidic compounds from the product such maybe accomplished by extracting the product with, for example, a 5% solution of,

sodiumhydroxide. The-extract will on acidificationyield oils boiling chiefly above 100 C. under 5 m. m. Hg. pressure and a residue will be obtained consisting largely of phenols, acids, ketonic bodies and polymerized products, I

ture within about the range:901C.-130 C. in'the presence of a chemical dehydrating agent, such as a dilute acid, iodin or fullers earth, for the purpose of converting the, terpineol into hydrocarbons. This treatment gives a producthaving a lower boiling range, which may render it more desirable for use in lacquers. produced by'dehydration may be separated by distillation leavinga high boiling productwhich colloids nitrocotton and which-may be employed as a plasticizer in lacquers. .As an example of thetreatment for dehydration of the ozonized product, say 500 cc. of alpha-terpineol may be ozonized for 10 hours at about 25 C. by passing throughit 2 litres of oxygen per minute, contain-' ing 20 mg. of ozone per litre. After partial decomposition by heating to about 125 0., it may be heated with 1' g. of iodin for a period of about 3 hours and at a temperature of about 120 C.

Approximately 75% of the product'will be c'onverted I into dipentene and other terpenes. On distillation ofi ofthe terpenes, a residue will remain boiling largely about 200 C. at 25 mm. This residue will desirably colloid nitrocotton. I

The heat-treated ozonized product, as has been I indicated, lends itself to'use as a solvent or col- ;l3utyl-v acetate loiding agent for nitrocellulose and may desirably be used as an ingredient of lacquers, containing nitrocellulose as an ingredient. When used as an ingredient. of lacquer, the,;heat-treated product may replace 'in part-other nitrocellulose solvents.

and, may .bejuse'd in varying proportions. The following formula will be illustrative -01" lacquer including ozonized heattreated terpineol;

I 1 r I Percent .Low ,viscositynitrocotton lO Denatured alcohol ...-1 5 Benzene- 25 Butanol' ,e l0 Ethyl, acetate;

Gum solution Ozonized and heat-treated terpineol I 7 I A lacquer including ozonized; heat-treated and dehydrated terpineol may be made in accordance with the following formula:

' 3 7 Percent Low viscosity nitrocotton 10 Ojzonized, heatgtreated and dehydrated. terp ineoI I 2.002.583 i j This application is filed as a division of the ap-' The hydrocarbons composition plication for United States Letters Patent for Improvement in ozonization products of terpene alcohols filed by me February 24, 1928, Serial No.

What I claim and desire toprotect by Letters Patentis:

.--1;"I'he products of a terpene alcohol having one double bond which has been ozonized, heattreated to'effect decomposition and then chemically dehydratedi l 2. The products of a terpineol which has been ozonized,, heat-treated to efiect decomposition and then chemically dehydrated.

3. The products'of alpha-terpineol which has been ozonized, heat-treated to effect decomposition and then chemically dehydrated.

then to heat treatment to efiect decomposition and finally to chemical dehydration.

6. The method of producing a composition of matter which includes subjecting a terpineol to ozonization, then to heat treatment. to effect deand finally to chemical dehydration. r

7; Themethod of producing a composition of matter which includes subjecting a terpineol to ozonization and subjecting the ozonized product to heat treatment to'efiect decomposition and then to treatment with a chemical dehydrating agent. 1

8..The method of-producing a composition of matter, which includes subjecting. a tepineol to ozonization and subjecting the ozonized product the rangeQO C.l3(l C. inthe presence of chemical dehydrating agent.

l9. Themethod of producing a composition of I matter which includes subjecting aterpineol to,

ozonizationand subjecting the ozonized product to heat treatment and then to treatment with I iodin. v '1 "10. 'The method of producing a composition of matter which includes subjecting a terpineol to ozonization and subjecting the ozonized product to heat treatment at a'temperature within about:

the-range C.-l30 C andthen'to treatment to effect decomposition at a temperature withinabout therange' 'C.130'C.'in the presence of iodin;

11. The products of'terpineol'which has been" composition and finally to chemical dehydration. b

LANNING PA K ANKIN, 

